Process for the preparation of alkaline sulfate esters of n-alkyl-substituted hydroxypolyalkoxymethylcyclohexenes

ABSTRACT

Nonionic biodegradable detergents may be prepared by condensing butadiene with allyl alcohol, thereafter ring alkylating the resultant hydroxymethylcyclohexene with an olefin in the presence of a free-radical generating compound to form an alkyl substituted hydroxymethylcyclohexene and alkoxylating this compound to form the desired product comprising a hydroxypolyalkoxymethylcyclohexenyl alkane.

United States Patent 1191 Bloch 1 1 Jan. 7, 1975 1 1 PROCESS FOR THE PREPARATION OF 2,236,919 4/1941 Reynhart 260/611 B ALKALINE SULFATE ESTERS 0}: 2,318,296 5/1943 Dickey 260/457 HYDROXYPOLYALKOXYMETHYLCY- 2,863,925 12/1958 Starcher 260/617 R CLOHEXENES Inventor: Herman S. Bloch, Skokie, Ill.

Universal Oil Products Company, Des Plaines, 111.

Filed: Aug. 3, 1972 Appl. No.: 277,835

Assignee:

References Cited UNITED STATES PATENTS 9/1939 Lubs 260/457 Bruson 260/617 R OTHER PUBLICATIONS Alder et al., Ber," Vol, 71B, pp. 1939, 1940 and 1949, (1938).

Primary Examiner-Leon Zitver Assistant Examiner-Norman P. Morgenstern Attorney, Agent, or Firm-James R. Hoatson, Jr.; Raymond H. Nelson; William H. Page, II

[57] ABSTRACT Nonionic biodegradable detergents may be prepared by condensing butadiene with allyl alcohol, thereafter ring alkylating the resultant hydroxymethylcyclohexene with an olefin in the presence of a free-radical generating compound to form an alkyl substituted hydroxymethylcyclohexene and alkoxylating this compound to form the desired product comprising a hydroxypolyalkoxymethylcyclohexenyl alkane.

2 Claims, No Drawings PROCESS FOR THE PREPARATION OF ALKALINE SULFATE ESTERS OF N-ALKYL-SUBSTITUTED HYDROXYPOLYALKOXYMETHYLCYCLOHEX- ENES This invention relates-to a process for preparing nonionic biodegradable detergents. More specifically, the invention is concerned with a novel method comprising a series of steps whereby hydroxypolyalkoxymethylcyclohexenyl alkanes, hydroxpolyalkoxymethylcyclohexyl alkanes or the corresponding alkaline sulfate esters are formed.

One of the major problems which is prevalent in population centers throughout the world is the disposal of sewage containing detergents dissolved therein. Such disposal problems are especially trying in the case of branch-chained alkylaryl detergents. These detergents produce stable foams in hard or soft waters in such large quantities that the foam clogs sewage treatment facilities, and destroys the bacteria which are necessary for proper sewage treatment. In many rivers, streams, lakes, etc. which act as a water supply for the aforesaid population centers, there are found these unwanted foams and suds. As hereinbefore set forth the presence of these unwanted foams or suds is due in many instances to the use of detergents which are nonbiodegradable in nature and which will not break down by bacterial action thereon. The non-biodegradable nature of these detergents is due to the fact that the alkyl side chain of the molecule is in many instances highly branched and therefore not readily attacked by the organisms which would ordinarily destroy the molecule. ln contradistinction to this, the use of straight chain alkyl substituents on the ring will permit the detergents to be destroyed and therefore foams or suds will not build up on the surface of the water.

It is therefore an object of this invention to provide a process for the production of detergents which show biodegradability in both urban and rural sewage disposal systems.

In one aspect an embodiment of this invention resides in a process for the preparation of a biodegradable detergent which comprises the steps of: (a) condensing butadiene with allyl alcohol in a Diels-Alder reaction at condensation conditions; (b) ring alkylating the resultant hydroxymethylcyclohexene with an olefin in the presence of a free-radical generating compound and hydrogen chloride at a temperature at least as high as the decomposition temperature of said free-radical generating compound, and (c) alkoxylating the resulting alkyl substituted hydroxymethylcyclohexene with an alkoxylating agent selected from the group consisting of ethylene oxide and propylene oxide to form the resultant hydroxypolyalkoxymethylcyclohexenyl alkane.

A specific embodiment of this invention is found in a process for the preparation of a biodegradable detergent which comprises the steps of condensing butadiene with allyl alcohol at a temperature in the range of from about 50 to about 190 C. and a pressure in the range of from atmospheric to about 100 atmospheres, ring alkylating the resultant hydroxymethylcyclohexene with l-octene in the presence of di-t-butyl peroxide and hydrogen chloride at a temperature at least as high as the decomposition temperature of said di-t-butyl peroxide, alkoxylating the resultant n-octyl hydroxymethylcyclohexene with ethylene oxide at a temperature in the range of from about 20 to about 125 C. and a pressure in the range of from about 25 to about 1,000 pounds per square inch in the presence of an acid or basic catalyst and recovering the resultant hydroxypolyethoxymethylcyclohexenyl n-octane.

Another specific embodiment of this invention is found in a process for the preparation of a biodegradable detergent which comprises the steps of condensing butadiene with allyl alcohol at a temperature in the range of from about 50 to about 190 C. and a pressure in the range of from atmospheric to about atmospheres, ring alkylating the resultant hydroxymethylcyclohexene with l-tetradecene in the presence of di-tbutyl peroxide and hydrogen chloride at a temperature at least as high as the decomposition temperature of said di-t-butyl peroxide, alkoxylating the resultant ntetradecyl hydroxymethylcyclohexene with ethylene oxide at a temperature in the range of from about 20 to about C. and a pressure in the range of from about 25 to about 1,000 pounds per square inch in the presence of an acidic or basic catalyst, sulfating the resultant hydroxypolyethoxymethylcyclohexenyl ntetradecane with sulfuric acid to form the sulfate ester thereof at a temperature in the range of from 0,to about 60 C., neutralizing said sulfate ester with sodium hydroxide at a temperature in the range of from about ambient to about 40 C. and recovering the resultant sodium sulfate ester of a hydroxypolyethoxymethylcyclohexenyl n-tetradecane.

Other objects and embodiments will be found in the following further detailed description of the present invention.

As hereinbefore set forth the present invention is concerned with a process for the preparation of detergents which are biodegradable in nature. In addition the present invention also contemplates the preparation of detergents which are nonionic or anionic in nature, the process for preparing these compounds being effected in a series of steps. In the first step of the reaction, butadiene is condensed with allyl alcohol in a Diels-Alder type condensation to give 4-hydroxymethylcyclohexene. The Diels-Alder condensation is effected at elevated temperatures, usually in the range of from about 50 to about C. and at a pressure ranging from atmospheric to about 100 atmospheres. The reaction pressure may be afforded by the autogenous pressure of the butadiene or by a combination of butadiene and a substantially inert gas such as nitrogen or argon, the amount of pressure which is utilized being that which is sufficient to maintain at least a portion of the reactants in the liquid phase.

The 4-hydroxymethylcyclohexene which has been prepared according to the above paragraph is recovered and selectively alkylated utilizing an olefinic hydrocarbon as the alkylating agent. The selective alkylation in which the alkyl substituent is positioned on the ring rather than on the side chain is effected by treating the reactants in the presence of a free-radical generating compound and hydrogen chloride. In the preferred embodiment of the invention, the olefinic hydrocarbon which is utilized as the alkylating agent will comprise a l-alkene containing from 3 to about 20 carbon atoms in length and preferably from about 6 to about 14 carbon atoms. By utilizing the l-alkene and an alkylation catalyst comprising a free-radical generating compound and a promoter comprising hydrogen chloride, it is possible to obtain a normal alkyl side chain on the 'cyclohexene ring rather than a secondary alkyl side chain which would result if the alkylation were effected in the presence of an acidic catalyst of the Friedel- Crafts type or sulfuric acid, etc. Specific examples of thea-olefinic hydrocarbons which are utilized as alkylating agents include propene, l-butene, l-pentene, 1- hexene, l-heptene, l-octene, l-nonene, l-decene, lundecene, l-dodecene, l-tri-decene, l-tetradecene, 1-pentadecene, l-hexadecene, l-heptadecene, loctadecene, 1 nonadecene, l-eicosene, etc.

The catalysts which are used in this step of the invention will include peroxy compounds, containing the bivalent radical'00, which decomposes to form free radicals which initiate the general reaction and are capable of inducing the condensation of the hydroxymethylcyclohexene with the l-alkene. Examples of these catalysts include the persulfates, perborates, percarbonates of ammonium and of the alkali metals, or organic peroxy compounds. The organic peroxy compounds constitute a preferred class of catalysts for use in the invention and include peracetic acid, persuccinic acid, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetyl peroxide, acetyl peroxide, dipropionyl peroxide, di-t-butyl peroxide, butyryl peroxide, lauroyl peroxide, benzoyl peroxide, tetralin peroxide, urea peroxide, t-butyl perbenzoate, tbutyl hydroperoxide, methylcyclohexyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, etc. Mixtures of peroxy compound catalysts may be employed or the peroxy compound catalyst may be utilized in admixture with various diluents. Thus, organic peroxy compounds which are compounds commercially with various diluents which may be used include benzoyl peroxide compounded with calcium sulfate, benzoyl peroxide compounded with camphor, phthalate esters, etc. Only catalytic amounts (less than stoichiometric amounts) need be used in the process.

The alkylation of the hydroxymethylcyclohexene with the l-alkene is effected at elevated reaction temperatures which should be at least as high as the initial decomposition temperature of the free-radical generating catalyst, such as the peroxide compound, in order to liberate and form free radicals which promote the reaction. In selecting a particular reaction temperature for use in the process of the present invention, two considerations must be taken into account. First sufficient energy by means of heat must be supplied to the reaction so that the reactants, namely the hydroxymethyl cyclohexene and the l-alkenes will be activated sufficiently for condensation to take place when free radicals are generated by the catalyst. Second, free-radical generating catalysts such as peroxy compounds, particularly organic'peroxide, decompose at a measurable rate with time in a logarithmic function dependent upon temperature. This rate of decomposition can be and ordinarily is expressed as the half life of a peroxide at a particular temperature. For example, the half life in hours for di-t-butyl peroxide is 11 hours at 125 C.,

4 hours at 135C., and 1.5 hours at 145 C. A reaction system temperature must then be selected so that the free-radical generating catalyst decomposes smoothly with the generation of free radicals at a half life which is not too long. In other words, sufficient free radicals must be present to induce the present chain reaction to take place, and these radicals must be formed at a temperature at which the reactants are in a suitably activated state for condensation. When the half life of the free-radical generating catalyst is greater than hours, radicals are not generated at a sufficient rate to cause the reaction of the process of the present invention to go forward at a practically useful rate. Thus the reaction temperature may be within the range of from about 50 to about 300 C. and at least as high as the decomposition temperature of the catalyst, by which is meant a temperature such that the half life of the freeradical generating catalyst is not greater than 10 hours.

Since the half life for each free-radical generating catalyst is different at different temperatures, the exact temperature to be utilized in a particular reaction will vary. However, persons skilled in the art are well acquainted with the half life vs. temperature data for different free-radical generating catalysts. Thus it is within the skill of one familiar with theart to select the particular temperature needed for any particular catalyst. However, the operating temperatures generally do not exceed the decomposition temperature of the catalyst by more than about C. since the free-radical generating catalysts decompose rapidly under such conditions. For example, when a free-radical generating catalyst such as t-butyl perbenzoate is used, having a 10 hour, 50% decomposition temperature of approximately C., the operating temperature of the process is from about 105 to about 205 C. When di-tbutyl peroxide having a decomposition temperature of about C. is used, the process is run at a temperature ranging from about 125 to about 225 C. Higher reaction temperatures may be employed, but little advantage is gained if the temperature is more than the hereinbefore mentioned 100 C. higher than the 10- hour, 50% decomposition temperature of the catalyst. The general effect of increasing the operating temperature is to accelerate the rate of condensation reaction of the hydroxymethylcyclohexene with the l-alkenes. However, the increased rate of reaction is accompanied by certain amounts of decomposition. In addition to the elevated temperatures which are utilized, the reaction may also be effected at elevated pressures ranging from 1 to about 100 atmospheres or more, the preferred operating pressure of the process being that which is required to maintain a substantial portion of the reactants in liquid phase. Pressure is not an important variable in the process of this invention. However, because of the low boiling points of some of the reactants it is necessary to utilize pressure-withstanding equipment to insure liquid phase conditions. In batch type operations it is often desirable to utilize pressurewithstanding equipment, to charge the reactants and the catalyst to the vessel and to pressure the vessel with 10 or 30 or 50 or more atmospheres of an inert gas such as nitrogen. This helps to insure the presence of liquid phase conditions. However, when the mole quantity of reactants is sufficient, the pressure which they themselves generate at the temperature utilized is sufficient to maintain the desired phase conditions.

I Furthermore, the concentration of the catalyst employed in this process may vary over a rather wide range but it is desirable to utilize low concentrations of catalysts such as from about 0.1% to about 10% of the total weight of the combined starting materials charged to the process. The reaction time may be within the range of from less than one minute to several hours, de-

pending upon temperature and the half life of the cata- In addition to the free-radical generating catalyst the alkylation is also effected in the presence of a hydrogen chloride compound. The hydrogen chloride compound is used as a promoter for the reaction and also is used to prevent or inhibit telomerization, said telomerization being a polymerization reaction in which unwanted side reaction products may be formed. The hydrogen chloride may be present as anhydrous hydrogen chloride, as concentrated hydrochloric acid or as an aqueous solution of hydrochloric acid, the hydrochloric acid being present in an amount of from 5% to about 38% in said aqueous solution.

As an alternative method in preparing the biodegradable detergents of the present invention, the hydroxymethylcyclohexene may be subjected to a selective hydrogenation step prior to alkylating the compound with a terminal olefin in the presence of a freeradical generating catalyst and hydrogen chloride as set forth in the preceding paragraph. When this method is employed, the final product will comprise a cyclohexyl product rather than a cyclohexenyl product which is obtained when omitting this step. When such an alternative method is followed, the hydroxymethylcyclohexene is selectively hydrogenated in the presence of a hydrogenation catalyst comprising a nickel-containing compound or a noble metal containing compound, these hydrogenation catalysts being well known in the art. Specific examples of these catalysts will include in particular platinum and palladium compounds per se or composited on a solid support which is essentially nonacidic in character such as charcoal or kieselguhr, nickel composited on kieselguhr, etc The reaction is effected at hydrogenation conditions which will include a temperature in the range of from about 25 up to about 100 C. and at an applied hydrogen pressure which may range from about 50 to about 2,000 pounds per square inch. When these conditions and catalysts are used, the hydroxymethyl substituent remains unchanged while the cyclohexene ring is hydrogenated to form a cyclohexane ring. Thereafter, the hydroxymethylcyclohexane may be subjected to ring alkylation by reaction with an a-olefin in the presence of the aforementioned free-radical generating compound and hydrogen chloride in a manner similar to that set forth in the above discussion. In an alternative variation of this procedure, the hydrogenation of the ring unsaturation may be carried out after the alkylation of the hydroxymethylcyclohexene, i.e. on the n-alkyl hydroxymethylcyclohexene.

The n-alkyl substituted hydroxymethylcyclohexane or n-alkyl substituted hydroxymethylcyclohexene is then subjected to an alkoxylation step to prepare nonionic detergents having the general structure:

in which R is a normal alkyl radical containing from 3 up to about carbon atoms, n is 2 or 3 and m is an integer ranging from about 1 to about 50 and preferably in a range of from about 3 to about 20. The alkoxylation of the n-alkyl substituted hydroxymethylcyclohexene or n-alkyl substituted hydroxymethylcyclohexane is effected by treating the compound with an alkoxylating agent selected from the group consisting of ethylene oxide and propylene oxide in an amount sufficient to produce the desired number of alkoxy units in order that the values hereinbefore set forth for m may be satisfied. In any event, a sufficient amount of alkylene oxide must be used to solubilize the product and maximize its surface active properties either without or with subsequent sulfation. Generally speaking, the value of m will be less when the finished product comprises a cyclohexene than will be needed with the corresponding cyclohexane compound, and will be lower when the product is to be sulfated than when it is to be used as an anionic detergent.

The alkoxylation is effected by treating the aforementioned compounds withthe ethylene oxide or propylene oxide at a temperature in the range of from about 20 (ambient) up to about C. and at a pressure in the range of from about 50 to about 1,000 pounds per square inch, the pressure being afforded by the alkoxylating agent. In addition the alkoxylating reaction is effected in the presence of an acidic or basic catalyst. Examples of acids which may be employed will include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, etc., organic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, etc. Examples of basic catalysts which may be employed will include sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium propionate, potassium propionate, lithium propionate, sodium hydroxide, potassium hydroxide, lithium hydroxide, the corresponding calcium compounds, magnesium compounds, etc. As hereinbefore set forth a sufficient amount of alkoxylating agent will be used in order that the predetermined value for m in the above formulas is satisfied. Therefore the alkoxylating agent will usually be present in the reaction mixture in a molar excess over that of the n-alkyl substituted hydroxymethylcyclohexene or cyclohexane, said molar excess usually being in a range of from about 5:1 to about 50:1 moles of alkylene oxide per mole of substituted cyclohexene or cyclohexane compound.

If so desired, in another embodiment of this invention, the n-alkyl substituted hydroxymethylcyclohexene or n-alkyl substituted hydroxymethylcyclohexane may be alkoxylated with a fewer number of moles of alkylene oxide, that is, generally from I to about 10 moles and preferably from I to about 5 moles and the resulting alkoxylated compound is then sulfated and neutralized to form anionic biodegradable detergents of the type:

in which R is an n-alkyl radical containing from 3 to about 20 carbon atoms, M is an alkali metal, alkaline earth metal or basic nitrogen-containing compound, n is an integer of 2 or 3 and m is an integer ranging from I to about 10. The sulfation of the hydroxypolyalkoxymethylcyclohexenyl alkane or corresponding cyclohexyl compound is accomplished by treating these compounds with a conventional sulfating agent such as sulfuric acid, oleum, sulfur trioxide, chlorosulfonic acid, etc. the temperatures ranging from about 0 to about 60 C. depending upon the type of sulfating agent which is used." For example when the sulfating a ent comprises sulfur trioxide or oleum the reaction ma be effected at a temperature in the subambient range that is, from to about 25 C. or if the sulfur trioxide is in gaseous form, the reaction may be effected at a temperature up to about 50 C. When utilizing sulfur trioxide in gaseous form, it is usually admixed with a sufficient amount of air so that the sulfur trioxide is present in an amount in the range of from 3 to about When employing other sulfating agents such as sulfuric acid, the reaction may be effected over the entire temperature range hereinbefore set forth, that is, from about 0 up to about 60 C. Likewise the use of chlorosulfonic acid as a sulfating agent will permit the reaction to be effected at ambient (20 to 25 C.) temperatures.

The sulfate ester of the h'ydroxypolyalkoxymethylcyclohexenyl alkane or hydroxypolyalkoxymethylcyclohexyl alkane is then neutralized by utilizing conventional neutralizing agents such as an alkali metal base, an alkaline earth metal base, ammonia or an amine. Specific examples of .these neutralizing agents will include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide,

magnesium hydroxide, calcium hydroxide, strontium hydroxide, ammonia, ammonium hydroxide, amines such as ethanolamine, propanol amine, benzyl amine, N,N-dimethylbe nzyl amine, N,N-diethylbenzyl amine,

methyl amine, ethyl amine, propyl amine, dimethyl' amine, diethyl amine, dipropyl amine, etc. Of the aforementioned neutralizing agents the preferred compounds comprise ammonium hydroxide, sodium hydroxide, or potassium hydroxide,'due to the greater availability and relatively lower cost of these compounds.

The neutralization reaction, being exothermic in nature, is usually effected under a controlled temperature system, the preferred temperature for the reaction being from aboutambient up to about 40 C. whereby the formation of undesired side products may be minimized. The control of the temperature of the neutralization reaction is usually effected by utilizing cooling means including ice baths, dry ice, cooling coils, etc. whereby the desired product is obtained.

The process of this invention in which biodegradable detergents of the type hereinbefore set forth in greater detail are prepared may be effected in either a batch or continuous operation. When a batch type operation is used, a quantity of the allyl alcohol is placed in an appropriate apparatus such as an autoclave of the rotating or mixing type. The autoclave is sealed and the butadiene is charged thereto or in an alternate method, a mixture of butadiene and an inert gas such as nitrogen is charged thereto until the desired operating pressure is reached. The autoclave is thereafter heated to the desired operating temperature within the range hereinbefore set forth and maintained thereat for a predetermined residence time which may range from 0.5 up to about 10 hours 'or more in duration. Upon completion of the desired residence time, heating is discontinued, the autoclave is allowed to return to room temperature, the excess pressure is vented and the reaction mixture is recovered therefrom. The hydroxymethylcyclohexene is separated from any unreacted allyl alcohol by conventional means such as distillation or by any other separation means known in the art and placed in a second reaction vessel along with a free-radical generating compound and the l-alkene which is to be utilized as the alkylating agent. This second reaction vessel may be a flask provided with condensing means or an autoclave of the rotating or mixing type. In addition, a promoter comprising hydrogen chloride either in gaseous form as hydrogen chloride or in aqueous form as hydrochloric acid is added to the reactor which is thereafter heated to the desired operating temperature which, as hereinbefore set forth, is at least as high as the decomposition temperature of said free-radical generating compound. After maintaining the alkylation reaction at this temperature for a predetermined period of time which may range from about 0.5 up to about 10 hours, heating is discontinued, the reaction mixture is allowed to return to room temperature and the n-alkyl substituted hydroxymethylcyclohexene is separated and recovered by conventional means.

Alternatively, if so' desired, the 4-hydroxymethylcyclohexene may be subjected to a hydrogenation step prior to alkylation with the l-alkene. If this step is to be employed, the hydroxymethylcyclohexene is selectively hydrogenated by passage over a catalyst of the type hereinbefore set forth in the presence of a hydrogen stream at a temperature ranging from about 25 to about C. and at a hydrogen pressure of from about 50 to about 2,000 pounds per square inch, the cyclohexene ring being selectively and relatively completely hydrogenated to form the corresponding cyclohexane ring. After separation from the hydrogen gas, the hydroxymethylcyclohexane is then treated with an alkylating agent such as'the l-alkene according to the method hereinbefore-set forth.

The n-alkyl substituted hydroxymethylcyclohexene or n-alkyl substituted hydroxymethylcyclohexane is then treated with an alkoxylating agent to form thedesired product. This treatment is accomplished by placing thesubstituted cyclohexene or substituted cyclohexane in an appropriate apparatus such as a rotating autoclave and the alkoxylating agent is added thereto in a predetermined molar excess so that the finished product will contain the requisite number of alkoxy units in the side chain. In addition, an acidic or basic catalyst of the type hereinbefore set forth in greater detail is also added to the apparatus which is thereafter heated to a predetermined operating temperature. After maintaining the apparatus and contents thereof at this temperature for a period of time which may range from'about 0.5 up to about 10 hours or more, the apparatus and contents thereof are allowed to return to room temperature and the product is recovered therefrom and sent to storage.

In the event'that an anionic detergent of the type hereinbefore set forth in greater detail comprises the desired product, the thus prepared hydroxypolyalkoxymethylcyclohexenyl alkane or hydroxypolyalkoxymethylcyclohexyl alkane is then treated with a sulfating agent to form the sulfate ester thereof. This treatment is accomplished by placing the alkane in an appropriate apparatus and adding thereto the sulfating agent. This apparatus may comprise a reaction flask if the sulfating agent, such as sulfuric acid or oleum, is in liquid form, or a pressure vessel if sulfur trioxide in gaseous form is vutilized as a sulfating agent. The sulfating reaction is effected at a temperature ranging from 0 to about 60 C., the reactor being cooled or heated according to the particular sulfating agent which is employed, said cooling or heating means which will be employed being of the conventional type such as cooling coils, ice baths, dry ice, or heating coils, etc. if elevated temperatures are employed. The sulfating agent is usually present in a molar excess over the alkane in order to insure complete sulfonation, said molar excess being in a range of from about 0.01:1 to about 1.521 moles of sulfating agent per mole of alkane.

The resultant sulfate ester is then neutralized by treatment with a compound of the type hereinbefore set forth. To accomplish this the sulfate ester is introduced into an appropriate apparatus also provided with cooling means in order to control the temperature of the reaction which, as hereinbefore set forth, is exothermic in nature. The neutralizing agent such as the alkali metal base, alkaline earth metal base, ammonia compound or amine is usually placed in the reactor in a molar excess over the sulfate ester, said excess being to insure the complete neutralization of the sulfate ester and the latter is gradually added, with vigorous stirring or agitation. The reaction is allowed to proceed while controlling the temperature thereof, said residence time also being in a range of from about 0.5 up to about 10 hours or more in duration. Upon completion of the desired residence time, the reaction mixture is recovered, and the water removed, whereby the desired alkaline sulfate ester of a hydroxypolyalkoxymethylcyclohexenyl alkane or alkaline sulfate ester of a hydroxypolyalkoxymethylcyclohexyl alkane is recovered. It is to be understood that for the purposes of this invention the term alkaline as used in the present specification and appended claims 'will include alkali metals, alkaline earth metals, ammonium or amine compounds.

It is also contemplated within the scope of this invention that the desired product may be prepared while employing a continuous manner of operation. When the continuous manner of operation is to be used, the starting materials comprising the allyl alcohol and butadiene are continuously charged to a reactor which is maintained at the proper operating conditions of temperature and pressure. After passage through this reactor for a predetermined period of time, the effluent is continuously withdrawn, subjected to a separation step whereby the unreacted allyl alcohol and butadiene are separated from the hydroxymethylcyclohexene and recycled to form a portion of the feed stock while the latter is continuously charged to an alkylation apparatus which is also maintained at the proper operating conditions of temperature and pressure. In addition the lalkene, the free-radical generating compound and the hydrogen chloride promoter are also continuously charged to the apparatus through separate lines or, if so desired, one or more of the reactants may be admixed with another prior to entry into said reactor and the resulting mixture charged thereto in a single stream. After completion of the desired residence time in the alkylation apparatus, the reactor effluent is continuously withdrawn, again subjected to separation steps whereby unreacted starting materials, promoter and by-products are separated from the alkyl substituted hydroxymethylcyclohexene. The unreacted starting materials are recycled to the apparatus to form a portion of the feed stock while the n-alkyl substituted hydroxymethylcyclohexene is continuously charged to the alkoxylation reactor. In this reactor the aforementioned cyclohexene is subjected to the action of an alkoxylating agent, said agent, either ethylene oxide or propylene oxide, being continuously charged to the reactor in a molar excess over the charge of the cyclohexene. In addition, the catalyst, either acidic or basic in nature, is also charged to the reactor through a separate line or, if so desired, it may be admixed with the carbinol feed and the resulting mixture charged thereto in a single stream. Upon completion of the desired residence time, the reactor effluent is withdrawn and, if desired, charged to a sulfating reactor. In this reactor the hydroxypolyalkoxymethylcyclohexenyl alkane is subjected to the action of a sulfating agent which is also continuously charged to this reactor, said reactor being maintained at the proper operating conditions, especially temperature. After passage through this reactor for a predetermined period of time, the effluent is continuously withdrawn, again subjected to separation steps whereby undesired impurities are separated from the sulfate ester, and the sulfate ester is continuously charged to the neutralization zone. In this zone the sulfate ester is subjected to the action of the neutralizing agent which is also continuously charged thereto. Inasmuch as, as hereinbefore set forth, the reaction is exothermic in nature, the temperature of the last named reactor is carefully maintained in a range of from about ambient up to about 40 C. in order that any unwanted side reactions are minimized and a higher yield of the desired product is obtained thereby. As in the prior steps in this continuous type of operation, the reactor effluent is continuously withdrawn and subjected to separation steps whereby the final product may be separated and recovered while any unreacted starting materials are recycled to the neutralization zone to form a portion of the feed stock thereto.

In the event that the desired biodegradable detergent comprises a di-substituted cyclohexane, the product resulting from the Diels-Alder condensation between the allyl alcohol and the butadiene is subjected to selective hydrogenation prior to the alkylation step with the l-alkene. The 4-hydroxymethylcyclohexene which is withdrawn from the first condensation zone, after being separated from unreacted allyl alcohol and butadiene, is continuously charged to a hydrogenation apparatus along with a stream of hydrogen sufficient to maintain the desired operation pressure. The hydrogen and the 4-hydroxymethylcyclohexene are continuously passed over a hydrogenation catalyst of the type hereinbefore set forth at a temperature in the range of from about 25 to about C. whereby the cyclohexene ring is selectively hydrogenated to form the corresponding cyclohexane ring, and the resulting product is continuously withdrawn. The product which has been selectively hydrogenated to form hydroxymethylcyclohexane is separated from hydrogen, which may be recycled to the hydrogenation step, while the former is thereafter charged to the alkylation reactor previously de scribed and subjected to the remaining steps in the process to form the desired product.

The following examples are given to illustrate the process of the present invention which, however, are not intended to limit the generally broad scope of the present invention in strict accordance therewith.

EXAMPLE I In this example 58 g. (1.0 mole) of allyl alcohol is placed in the glass liner of a rotating autoclave. The liner is sealed into the autoclave and 54 g. (1.0 mole) of butadiene is charged thereto. The autoclave is then heated to a temperature of 125 C. and maintained thereat for a period of 4 hours, at the end of which time heating is discontinued, and the autoclave is allowed to return to room temperature. The autoclave is opened, the reaction mixture is recovered therefrom and subjected to fractional distillation whereby the desired product comprising 4-hydroxymethylcyclohexene is separated from any unreacted allyl alcohol and recovered.

The 4-hydroxymethycyclohexene which is prepared according to the above paragraph is then placed in the glass liner of a rotating autoclave along with the alkylating agent comprising l-octene, the charge stock consisting of a molar excess of the hydroxymethylcyclohexene over the l-octene in a range of from about 1.511 to about 2:1 moles of hydroxymethylcyclohexene per mole of l-octene. In addition 7 g. of di-t-butyl peroxide and 20 g. of concentrated hydrochloric acid which acts as a promoter are also placed in the autoclave. The liner is sealed into the autoclave and nitrogen is pressed in until an initial operating pressure of 30 atmospheres is reached. Thereafter the autoclave and contents thereof are heated to a temperature of 130 C. and maintained in a range of from 130 to 140 C. for a period of 8 hours. At the end of the 8-hour period, heating is discontinued, the autoclave is allowed to return to room .temperature and the excess pressure is discharged therefrom. The autoclave is then opened, the reaction mixture is recovered and subjected to fractional distillation, usually under reduced pressure, whereby the desired product comprising the n-octyl substituted 4-hydroxymethylcyclohexene is separated from unreacted starting materials, acid, etc. and recovered.

The n-octyl substituted hydroxymethylcyclohexene which is recovered according to the method set forth in the above paragraph is then placed in an autoclave and a catalytic amount of sodium carbonate is added to the reactor which is thereafter sealed. A molar excess of ethylene oxide comprising about 9 moles of ethylene oxide per mole of n-octyl substituted hydroxymethylcyclohexene is then pressured in, and the autoclave is heated to a temperature of 50 C. At the end of the 4- hour period, heating is discontinued, the autoclave is allowed to return to room temperature, the excess pressure is discharged and the hydroxypolyethoxymethylcyclohexenyl n-octane is recovered.

EXAMPLE II In this example a mole proportion of allyl alcohol is placed in the glass liner of a rotating autoclave which is thereafter sealed and a mole proportion of butadiene along with a sufficient amount of nitrogen is pressed into the autoclave until an initial pressure of 30 atmospheres is reached. The autoclave and contents thereof are then heated to a temperature'of 140 C. and maintained in a range of from 135 to 140 C. for a period of 4 hours. At the end of the 4-hour period, heating is discontinued, the autoclave is allowed to return to room temperature and the excess pressure is discharged therefrom. The autoclave is opened, the reaction mixture is recovered and subjected to fractional distillation under reduced pressure whereby the desired .product comprising 4-hydroxymethylcyclohexene is separated and recovered.

The hydroxymethylcyclohexene which is prepared according to the above paragraph is then placed in the glass liner of a rotating autoclave along with 1- tetradecene, the hydroxymethylcyclohexene being present in a molar excess over the l-tetradecene. In addition, a catalyst comprising 7 g. of di-t-butyl peroxide and a promoter comprising 20 g. of hydrochloric acid is also added to the liner. The liner is then sealed into the autoclave and nitrogen is pressed in until an initial operating pressure of 30 atmospheres is reached. The autoclave and contents thereof are then heated to a temperature of 130 C. and maintained in a range of from 130 to 140 C. for a period'of 8 hours. At the end of this period, heating is discontinued, the autoclave is allowed to return to room temperature, the excess pressure is discharged and the autoclave is opened. After recovery of the reaction mixture it is subjected to fractional distillation under reduced pressure whereby the n-tetradecyl substituted 4-hydroxymethylcyclohexene is recovered.

The aforementioned n-tetradecyl substituted hydroxymethylcyclohexene is placed in the glass liner of a rotating autoclave along with propylene oxide in a mole ratio of 8 moles of propylene oxide per mole of substituted cyclohexene. In addition a catalytic amount of sodium carbonate is also added to the liner which is thereafter sealed in the autoclave and the resulting mixture heated to a temperature of 50 C. for a period of 4 hours. At the end of this time, heating is discontinued, the excess pressure is discharged and the desired biodegradable detergent comprising a hydroxypolypropoxymethylcyclohexenyl n-tetradecane is recovered therefrom.

EXAMPLE III The first step of the process for preparing the desired product is effected in a manner similar to that hereinbefore set forth, that is, the 4-hydroxymethylcyclohexone is prepared in a Diels-Alder reaction by condensing allyl alcohol and butadiene. The thus prepared hydroxymethylcyclohexene is then charged to a reactor which is loaded with a catalyst comprising platinum composited on granular charcoal. The 4-hydroxymethylcyclohexene is charged to the reactor ata liquid gen in an amount sufficient to maintain a hydrogen pressure of 1,000 pounds per square inch, the temperature of the reaction being maintained at 40 C. After passage over the catalyst, the effluent stream is withdrawn to a separation zone wherein the hydrogen gas is separated from the liquid phase, which, upon analysis, is foundto be substantially fully hydrogenated to the desired product, hydroxymethylcyclohexane.

The hydroxymethylcyclohexane along with l-octene, a catalyst comprising di-t-butylperoxide and concentrated hydrochloric acid is placed in the glass liner of a rotating autoclave and after sealing the autoclave nitrogen is pressed in until an initial pressure of 30 atmospheres is reached. The autoclave and contents thereof are then heated to a temperature of C. and maintained in a range of from 130 to [40 C. for a period of 8 hours. At the end of this time, heating is discontinued, the autoclave is-allowed to return to room temperature and the excess pressure is discharged therefrom. The autoclave is opened, the reaction product is recovered and subjected to conventional means of separation whereby the n-octyl substituted hydroxymethylcyclohexane is separated and recovered.

The aforementioned n-octyl substituted hydroxymethylcyclohexane is then placed in the glass liner of an autoclave along with a catalyst comprising potassium carbonate. A molar excess of ethylene oxide, in a mole ratio of moles of ethylene oxide per mole of n-octyl substituted hydroxymethylcyclohexane, is then pressed into the sealed autoclave, and the reactor heated to a temperature of 100 C. for a period of 4 hours. At the end of this time, heating is discontinued, the autoclave is allowed to return to room temperature and the excess pressure is discharged therefrom. The autoclave is opened, and the desired product comprising a hydroxypolyethoxymethylcyclohexyl n-octane is recovered therefrom.

EXAMPLE IV In this example 4-hydroxymethylcyclohexene is prepared in a manner similar to that hereinbefore set forth, that is, by condensing allyl alcohol and butadiene in a Diels-Alder reaction. The thus prepared hydroxymethylcyclohexene is thereafter alkylated by treating a mole excess of the hydroxymethylcyclohexene with 1- octene in the presence of di-t-butyl peroxide and concentrated hydrochloric acid at a temperature of 130 C. and a nitrogen pressure of 30 atmospheres for a period of 8 hours. The n-octyl hydroxymethylcyclohexene which is prepared according to this step is then alkoxylated by reaction with ethylene oxide, the mole ratio of ethylene oxide to substituted cyclohexene being 3 moles of ethylene oxide per mole of substituted cyclohexene. The resultant hydroxypolyethoxymethylcyclohexenyl n-oetane is then placed in a reaction flask and treated with a molar excess of concentrated sulfuric acid, the addition of the acid being carried out at a slow rate during a period of 1 hour. Upon completion of the addition of the sulfuric acid, the mixture is stirred for an additional period of 1 hour, the temperature of the reaction being maintained at room temperature by means of cooling coils. The thus formed sulfate ester of the hydroxypolyethoxymethylcyclohexenyl noctane is then neutralized by treatment with a molar excess of sodium hydroxide, said sodium hydroxide being slowly added to the sulfate ester during a period of about 1 hour with continuous stirring and control of the exothermic nature of the reaction by cooling coils. Upon completion of the addition of the sodium hydroxide, the mixture is stirred for an additional l-hourperiod and the desired product comprising the sodium sulfate ester of a hydroxypolyethoxymethylcyclohexenyl n-octane is recovered.

EXAMPLE V To a reactor which has been loaded with a hydrogenation catalyst comprising nickel composited on kieselguhr is charged 4-hydroxymethylcyclohexene which is prepared from the Diels-Alder condensation of allyl alcohol and butadiene in a manner similar to that hereinbefore set forth. The 4 hydroxymethylcyclohexene is charged to the reactor at a temperature of about 40 C. and a liquid hourly space velocity of 1 along with a stream of hydrogen sufficient to maintain a hydrogen pressure of 1,000-pounds per square inch. After passage over the catalyst the effluent stream is withdrawn to a separation zone wherein the hydrogen gas is separated from the liquid phase which comprises the selectively hydrogenated product, namely, hydroxymethylcyclohexane.

A molar excess of the aforementioned hydroxymethylcyclohexane along with l-octene, benzoyl peroxide and concentrated hydrochloric acid are placed in an alkylation apparatus and heated to a temperature in the range of from to C. for a period of 4 hours. At the end of the 4-hour period, heating is discontinued, the reactor is allowed to return to room temperature and the mixture is subjected to fractional distillation whereby the desired product comprising n-octyl substituted hydroxymethylcyclohexane is recovered.

This compound is then placed in a glass liner of a rotating autoclave along with a catalytic amount of hydrochloric acid. Ethylene oxide is then pressed into the reactor in a mole ratio of 4 moles of ethylene oxide per mole of substituted cyclohexane, and the reactor is thereafter sealed and heated to a temperature of 75 C. for a period of 4 hours. At the end of this period, heating is discontinued, the autoclave is allowed to return to room temperature, the excess pressure is discharged and the reaction mixture is recovered. The hydroxypolyethoxymethylcyclohexyl n-octane is recovered and treated with an excess of sulfuric acid in a manner similar to that set forth in Example IV above. Thereafter the resulting sulfate ester is neutralized with a molar excess of sodium hydroxide during a period of 2 hours in which the sodium hydroxide is slowly added with continuous stirring to the sulfate ester while maintaining the temperature at about 25 C. by means of cooling coils. Upon completion of the 2-hour period, the desired product comprising the sodium sulfate ester of a hydroxypolyethoxymethylcyclohexyl n-octane is recovered.

I claim as my invention:

1. A process for the preparation of a biodegradable detergent which comprises the steps of:

a. condensing butadiene with allyl alcohol in a Diels- Alder reaction at a temperature in the range of from about 50 to about 190C. and a pressure in the range of from atmospheric to about atmospheres to form hydroxymethylcyclohexene;

b. selectively hydrogenating the hydroxymethylcyclohexene to form hydroxymethylcyclohexane;

0. ring alkylating the resultant hydroxymethylcyclohexane with an l-alkene in the presence of an organic peroxy free-radical generating compound and hydrogen chloride at a temperature at least as high as the decomposition temperature of said freeradical generating compound,

d. alkoxylating the resulting n-alkyl substituted hydroxymethylcyclohexane with an alkoxylating agent selected from the group consisting of ethylene oxide and propylene oxide at a temperature in the range of from about 20 up to about C. and at a pressure of from about 50 to about 1,000 pounds per square inch to form the resultant nalkyl-substituted hydroxypolyalkoxymethylcyclohexane;

. sulfating said n-alkyl-substituted hydroxypolyalkoxymethylcycloheane with a sulfating agent at a temperature of from about 0 to about 60C. to form the sulfate ester thereof and neutralizing said sulfate ester with a neutralizing agent to form the alkaline sulfate ester of said n-alkyl-substituted hydroxypolyalkoxymethylcycloheane.

2. The process as set forth in claim 1 in which said 1 alkene is l-octene, said alkoxylating agent is ethylene oxide, said sulfating agent is sulfuric acid, said neutralizing agent is sodium hydroxide and the alkaline sulfate ester of an n-alkyl-substituted hydroxypolyalkoxymethylcycloheane is the sodium sulfate ester of an n-octyl hydroxypolyethoxymethylcyclohexane. 

1. A PROCESS FOR THE PREPARATION OF A BIDEGRADABLE DETERGENT WHICH COMPRISES THE STEPS OF: A. CONDENSING BUTADIENE WITH ALLYL ALCOHOL IN A DIELS-ALDER REACTION AT A TEMPERATURE IN THE RANGE OF FROM ABOUT 50* TO ABOUT 190*C. AND A PRESSURE IN THE RANGE OF FROM ATMOSPHERE TO ABOUT 100 ATMOSPHERES TO FORM HYDROXYMETHYLCYCLOHEXANE; B. SELECTIVELY HYDROGENATING THE HYDROXMETHYLCYCLOHEXANE TO FORM HYDROXYMETHYCYCLOHEXANE; C. RING ALKYLATING THE RESULTANT HYDROXYMETHYLCYCLOHEXANE WITH AN 1-ALKENE IN THE PRESENCE OF AN ORGANIC PEROXY FREE-RADICAL GENERATING COMPOUND AND HYDROGEN CHLORIDE AT A TEMPERATURE AT LEAST AS HIGH AS THE DECOMPOSITION TEMPERATURE OF SAID FREE-RADICAL GENERATING COMPOUND, D. ALKOXYLATING THE RESULTING N-AKLYL SUBSTITUTED HYDROXYMETHYLCYCLOHEXANE WITH AN ALKOXYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF ETHYLENE OXIDE AND POPYLENE OXIDE AT A TEMPERATURE IN THE RANGE OF FROM ABOUT 20* UP TO ABOUT 125*C AND AT A PRESSURE OF FROM ABOUT 50 TO ABOUT 1,000 POUNDS PER SQUARE INCH TO FORM THE RESULTANT N-ALKYL-SUBSTITUTED HYDROXYPOLYALKOXYMETHYLCYCLOHEXANE; E. SULFATING SAID N-ALKYL-SUBSTITUTED HYDROXYPOLYALKOXYMETHYLCYCLOHEANE WITH A SULFATING AGENT AT A TEMPERATURE OF FROM ABOUT 0* TO ABOUT 60*C, TO FORM THE SULFATE ESTER THEREOF AND NETURALIZING SAID SULFATE ESTER WITH A NETURALIZING AGENT TO FORM THE ALKALINE SULFATE ESTER OF SAID N-ALKYLSUBSTITUTED HYDROXYPOLYALKOXYMETHYLCYCLOHEANE.
 2. The process as set forth in claim 1 in which said 1-alkene is 1-octene, said alkoxylating agent is ethylene oxide, said sulfating agent is sulfuric acid, said neutralizing agent is sodium hydroxide and the alkaline sulfate ester of an n-alkyl-substituted hydroxypolyalkoxymethylcycloheane is the sodium sulfate ester of an n-octyl hydroxypolyethoxymethylcyclohexane. 